Sulphonylaminocarbonyltriazolinones having halogenoalkylthio substituents

ABSTRACT

The invention relates to novel sulphonylaminocarbonyltriazolinones of the formula (I), ##STR1## in which R 1  represents hydrogen, hydroxyl, amino, alkylideneamino or a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkylalkyl, cycloalkylamino, aryl, arylalkyl, 
     R 2  represents respectively halogen-substituted alkyl or alkenyl and 
     R 3  represents a respectively optionally substituted radical from the group consisting of alkyl, aralkyl, aryl, heteroaryl, 
     and to salts of compounds of the formula (I), to processes and novel intermediates for preparing the compounds (I) and to their use as herbicides and/or fungicides.

This application is a divisional of application Ser. No. 08/894,932, filed on Nov. 17, 1997, now U.S. Pat. No. 5,994,273, issued Nov. 30, 1999, which is a 371 of PCT/EP96/00834, filed on Mar. 1, 1996.

The invention relates to novel sulphonylaminocarbonyltriazolinones having halogenoalkylthio substituents, to a plurality of processes and novel intermediates for their preparation and to their use as herbicides and fungicides.

Certain sulphonylaminocarbonyltriazolinones are already known to have herbicidal properties (cf. EP-A 34148, EP-A 422469, EP-A 425948, EP-A 431291, EP-A 507171). However, the activity of these compounds is not in all aspects satisfactory.

This invention accordingly provides the novel sulphonylaminocarbonyltriazolinones having halogenoalkylthio substituents of the general formula (I) ##STR2##

in which

R¹ represents hydrogen, hydroxyl, amino, alkylideneamino or a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkylalkyl, cycloalkylamino, aryl, arylalkyl,

R² represents respectively halogen-substituted alkyl or alkenyl and

R³ represents a respectively optionally substituted radical from the group consisting of alkyl, aralkyl, aryl, heteroaryl,

and salts of compounds of the formula (I).

The novel sulphonylaminocarbonyltriazolinones having halogenoalkylthio substituents of the general formula (I) are obtained when

(a) triazolinones of the general formula (II) ##STR3##

in which

R¹ and R² are each as defined above

are reacted with sulphonyl isocyanates of the general formula (III)

    R.sup.3 --SO.sub.2 --N═C═O                         (III)

in which

R³ is as defined above,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or

(b) triazolinone derivatives of the general formula (IV) ##STR4##

in which

R¹ and R² are each as defined above and

Z represents halogen, alkoxy, aralkoxy or aryloxy are reacted with sulphonamides of the general formula (V)

    R.sup.3 --SO.sub.2 --NH.sub.2                              (V)

in which

R³ is as defined above,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or

(c) triazolinones of the general formula (II) ##STR5##

in which

R¹ and R² are each as defined above

are reacted with sulphonamide derivatives of the general formula (VI)

    R.sup.3 --SO.sub.2 --NH--CO--Z                             (VI)

in which

R³ is as defined above and

Z represents halogen, alkoxy, aralkoxy or aryloxy,

if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or

(d) triazolinones of the general formula (II) ##STR6##

in which

R¹ and R² are each as defined above

are reacted with sulphonyl halides of the general formula (VII)

    R.sup.3 --SO.sub.2 --X                                     (VII)

in which

R³ is as defined above and

X represents halogen

and metal cyanates of the general formula (VIII)

    MOCN                                                       (VIII)

in which

M represents an alkali metal or an alkaline earth metal equivalent,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

and the compounds of the formula (I) obtained by process (a), (b), (c) or (d) are, if required, converted by customary methods into salts.

The novel sulphonylaminocarbonyltriazolinones having halogenoalkylthio substituents of the general formula (I) have strong herbicidal and/or fungicidal activity.

The invention preferably provides compounds of formula (I) in which

R¹ represents hydrogen, hydroxyl, amino, C₁ -C₆ -alkylideneamino, or optionally fluorine-, chlorine-, bromine-, cyano-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkyl-carbonyl- or C₁ -C₄ -alkoxy-carbonyl-substituted C₁ -C₆ -alkyl, or respectively optionally fluorine-, chlorine- and/or bromine-substituted C₂ -C₆ -alkenyl or C₂ -C₆ -alkinyl, or respectively optionally fluorine- and/or chlorine-substituted C₁ -C₆ -alkylamino, di-(C₁ -C₄ -alkyl)-amino or C₁ -C₄ -alkanoylamino, or respectively optionally fluorine-, chlorine-, bromine- and/or C₁ -C₄ -alkyl-substituted C₃ -C₆ -cycloalkyl or C₃ -C₆ -cycloalkyl-C₁ -C₄ -alkyl, or respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C₁ -C₄ -alkyl-, trifluoromethyl-, C₁ -C₄ -alkoxy- and/or C₁ -C₄ -alkoxy-carbonyl-substituted phenyl or phenyl-C₁ -C₄ -alkyl,

R² represents respectively fluorine-, chlorine- and/or bromine-substituted C₁ -C₆ -alkyl or C₂ -C₆ -alkenyl and

R³ represents the grouping ##STR7##

in which

R⁴ and R⁵ are identical or different and each represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, C₁ -C₆ -alkyl, (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)amino-carbonyl, hydroxyl, C₁ -C₄ -alkoxy, formyloxy, C₁ -C₄ -alkylcarbonyloxy, C₁ -C₄ -alkoxy-carbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkyl-sulphonyl, di-(C₁ -C₄ -alkyl)-aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl), or C₂ -C₆ -alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxycarbonyl, carboxyl or phenyl), or C₂ -C₆ -alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl or phenyl), or C₁ -C₄ -alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), or C₁ -C₄ -alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), or C₂ -C₆ -alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl), or C₂ -C₆ -alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₃ -alkylthio or C₁ -C₄ -alkoxycarbonyl), C₃ -C₆ -alkinyloxy, C₃ -C₆ -alkinylthio or the radical --S(O)_(p) --R⁶, where

p represents the numbers 1 or 2 and

R⁶ represents C₁ -C₄ -alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino, phenyl or the radical --NHOR⁷, where

R⁷ represents C₁ -C₁₂ -alkyl (which is optionally substituted by fluorine, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkcylsulphinyl, C₁ -C₄ -alkylsulphonyl, C₁ -C₄ -alkyl-carbonyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylamino-carbonyl or di-(C₁ -C₄ -alkyl)-amino-carbonyl), or C₃ -C₆ -alkenyl (which is optionally substituted by fluorine, chlorine or bromine), C₃ -C₆ -alkinyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₂ -alkyl, phenyl-C₁ -C₂ -alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkoxy-carbonyl), or benzohydryl or phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₄ -alkylthio, trifluoromethylthio or C₁ -C₄ -alkoxy-carbonyl),

R⁴ and/or R⁵ farther each represent phenyl or phenoxy, or C₁ -C₄ -alkyl-carbonylamino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkylamino-carbonyl-amino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, or the radical --CO--R⁸, where

R⁸ represents hydrogen, C₁ -C₆ -alkyl, C₃ -C₆ -cycloalkyl, C₁ -C₆ -alkoxy, C₃ -C₆ -cycloalkoxy, C₃ -C₆ -alkenyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, C₁ -C₄ -alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino or di-(C₁ -C₄ -alkyl)-amino (each of which are optionally substituted by fluorine and/or chlorine),

R⁴ and/or R⁵ further each represent trimethylsilyl, thiazolinyl, C₁ -C₄ -alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-amino-sulphonylamino or the radical

--CH═N--R⁹, where

R⁹ represents optionally fluorine-, chlorine-, cyano-, carboxyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio-, C₁ -C₄ -alkylsulphinyl- or C₁ -C₄ -alkylsulphonyl-substituted C₁ -C₆ -alkyl, or optionally fluorine- or chlorine-substituted benzyl, or optionally fluorine- or chlorine-substituted C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl, or optionally fluorine-, chlorine-, bromine-, C₁ -C₄ -alkyl-, C₁ -C₄ -alkoxy-, trifluoromethyl-, trifluoromethoxy- or trifluoro-methylthio-substituted phenyl, or optionally fluorine- and/or chlorine-substituted C₁ -C₆ -alkoxy, C₃ -C₆ -alkenoxy, C₃ -C₆ -alkinoxy or benzyloxy, or amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino, phenylamino, C₁ -C₄ -alkyl-carbonyl-amino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkyl- sulphonylamino or optionally fluorine-, chlorine-, bromine- or methyl-substituted phenylsulphonylamino,

furthermore

R³ represents the radical ##STR8##

in which

R¹⁰ represents hydrogen or C₁ -C₄ -alkyl,

R¹¹ and R¹² are identical or different and each represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, C₁ -C₄ -alkoxy-carbonyl, dim ethylaminocarbonyl, C₁ -C₄ -alkylsulphonyl or di-(C₁ -C₄ -alkyl)-aminosulphonyl;

furthermore

R³ represents the radical ##STR9##

in which

R¹³ and R¹⁴ are identical or different and each represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine) or C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine);

furthermore

R³ represents the radical ##STR10##

in which

R¹⁵ and R¹⁶ are identical or different and each represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), or C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), or aminosulphonyl, mono-(C₁ -C₄ -alkyl)-aminosulphonyl, or di-(C₁ -C₄ -alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl or dimethylaminocarbonyl;

furthermore

R³ represents the radical ##STR11##

in which

R¹⁷ and R¹⁸ are identical or different and each represent hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or bromine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), or C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (each of which are optionally substituted by fluorine and/or chlorine), or di-(C₁ -C₄ -alkyl)-aminosulphonyl;

furthermore

R³ represents the radical ##STR12##

in which

R¹⁹ and R²⁰ are identical or different and each represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C₁ -C₄ -alkyl)-amino-sulphonyl, C₁ -C₄ -alkoxy-carbonyl or dimethylaminocarbonyl, and

A represents oxygen, sulphur or the grouping N--Z¹, where

Z¹ represents hydrogen, C₁ -C₄ -alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C₃ -C₆ -cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl or di-(C₁ -C₄ -alkyl)-aminocarbonyl;

furthermore

R¹ represents the radical ##STR13##

in which

R²¹ and R²² are identical or different and each represent hydrogen, C₁ -C₄ -alkyl, halogen, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy or C₁ -C₄ -halogenoalkoxy,

Y¹ represents sulphur or the grouping N--R²³, where

R²³ represents hydrogen or C₁ -C₄ -alkyl;

furthermore

R³ represents the radical ##STR14##

in which

R²⁴ represents hydrogen, C₁ -C₄ -alkyl, benzyl, pyridyl, quinolyl or phenyl,

R²⁵ represents hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or C₁ -C₄ -alkoxy-carbonyl and

R²⁶ represents hydrogen, halogen or C₁ -C₄ -alkyl.

Furthermore, the invention preferably provides sodium, potassium, magnesium, calcium, ammonium, C₁ -C₄ -alkyl-ammonium, di-(C₁ -C₄ -alkyl)-ammonium, tri-(C₁ -C₄ -alkyl)-ammonium, tetra-(C₁ -C₄ -alkyl)-ammonium, tri-(C₁ -C₄ -alkyl)-sulphonium, C₅ - or C₆ -cycloalkyl-ammonium and di-(C₁ -C₂ -alkyl)-benzylammonium salts of the compounds of the formula (I) in which n, R¹, R² and R³ each have the preferred meanings given above.

The invention in particular provides compounds of the formula (I) in which

R¹ represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, or methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, or respectively optionally fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or respectively optionally fluorine-, chlorine-, bromine-, cyano-, methyl-, trifluoromethyl- or methoxy-substituted benzyl or phenyl,

R² represents respectively fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl or butenyl and

R³ represents the radical ##STR15##

in which

R⁴ represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, n- or i-butoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2,2,2-trifluoro-ethoxy, 1,1,2,2-tetrafluoro-ethoxy, 1,1,2,2,2-pentafluoro-ethoxy, 2-methoxy-ethoxy, methylthio, ethylthio, n- or i-propylthio, n-or i-butylthio, 2-fluoro-ethylthio, allyloxy, propargyloxy, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylamino-sulphonyl, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and

R⁵ represents hydrogen, methyl, ethyl, fluorine, chlorine or bromine;

furthermore

R³ represents the radical ##STR16##

in which

R¹⁰ represents hydrogen,

R¹¹ represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and

R¹² represents hydrogen;

furthermore

R³ represents the radical ##STR17##

in which

R represents methyl, ethyl, n- or i-propyl, or

R³ represents the radical ##STR18##

in which

R²⁴ represents methyl, ethyl, n- or i-propyl, phenyl or pyridyl,

R²⁵ represents hydrogen, fluorine, chlorine or bromine and

R²⁶ represents fluorine, chlorine, bromine, methoxycarbonyl or ethoxycarbonyl.

The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the precursors or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, thus including combination between the preferred ranges indicated.

In the definitions of the radicals, hydrocarbon radicals such as alkyl, alkenyl or alkinyl are straight-chain or branched, even in combinations with hetero atoms, as in alkoxy, alkylthio or alkylamino, even if this is not explicitly stated

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

Using, for example, 2-trifluoromethoxy-phenylsulphonyl isocyanate and 4-ethyl-5-difluoromethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following equation: ##STR19##

Using, for example, 2-ethylthio-benzenesulphonamide and 2-chlorocarbonyl-4-cyclopropyl-5-(2,2-difluoro-ethylthio)-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (b) according to the invention can be illustrated by the following equation: ##STR20##

Using, for example, N-methoxycarbonyl-2-methoxy-benzenesulphonamide and 5-(2-chloro-ethylthio)-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (c) according to the invention can be illustrated by the following equation: ##STR21##

Using, for example, 2-chloro-6-methyl-benzenesulphonyl chloride, 4-allyl-5-(2,3,3-trifluoro-propylthio)-2,4-dihydro-3H-1,2,4-triazol-3-one and sodium cyanate as starting materials, the course of the reaction in the process (d) according to the invention can be illustrated by the following equation: ##STR22##

A general definition of the triazolinones to be used as starting materials in the processes (a), (c) and (d) according to the invention for preparing compounds of the formula (I) is given by the formula (II).

In the formula (II), R¹ and R² each preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for R¹ and R².

The triazolinones of the general formula (II) have not been disclosed in the literature; as novel substances, they also form part of the subject matter of the present application.

The novel triazolinones of the general formula (II) are obtained when mercaptotriazolinones of the general formula (IX) ##STR23##

in which

R¹ is as defined above

--and/or the corresponding isomeric thiourazoles and/or the corresponding metal salts, in particular sodium salts or potassium salts--

are reacted with alkylating agents of the general formula (X)

    X.sup.1 --R.sup.2                                          (X)

in which

R² is as defined above and

X¹ represents halogen, preferably chlorine, bromine or iodine,

if appropriate in the presence of an acid acceptor, such as, for example, sodium hydroxide, and in the presence of a diluent, such as, for example dioxane, methanol, ethanol, n- or i-propanol and/or water, at temperatures between 0° C. and 100° C. (cf the preparation examples).

The intermediates of the formula (IX) are known and/or can be prepared by conventional processes (cf EP-A 43 1291; DE-A 2250572; J. Heterocycl. Chem. 15 (1978), 377-384).

The intermediates of the formula (X) are also known and/or can be prepared by conventional processes (cf J. Fluorine Chem. 13 (1979), 325; loc. cit. 20 (1982), 637; loc. cit. 21 (1982), 253; loc. cit 28 (1985), 291); J. Chem. Soc., Perkin II 1975, 1841).

A general definition of the sulphonyl isocyanates also to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I) is given by the formula (III).

In the formula (III), R³ preferably or in particular has that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for R³.

The starting materials of the formula (III) are known and/or can be prepared by methods known per se (cf. U.S. Pat. No. 4,127,405, U.S. Pat. No. 4,169,719, U.S. Pat. No. 4,371,391, EP-A7687, EP-A 13480, EP-A21641, EP-A23141, EP-A23422, EP-A30139, EP-A 35893; EP-A 44808; EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A 173312).

A general definition of the triazolinone derivatives to be used as starting materials in the process (b) according to the invention for preparing compounds of the general formula (I) is given by the formula (IV). In the formula (IV), RI and R² each preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I), as being preferable or particularly preferable for R¹ and R² ; Z preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or nitro-phenoxy, and in particular represents methoxy, phenoxy or 4-nitro-phenoxy.

The starting materials of the formula (IV) have not been disclosed in the literature; as novel substances, they also form part of the subject matter of the present application.

The novel compounds of the formula (IV) are obtained when triazolinones of the general formula (II) ##STR24##

in which

R¹ and R² are each as defined above,

are reacted with carbonic acid derivatives of the general formula (XIII)

    Z--CO--Z.sup.1                                             (XIII)

in which

Z is as defined above and

Z¹ represents halogen, alkoxy, aralkoxy or aryloxy,

if appropriate in the presence of an acid acceptor, such as, for example, sodium hydride or potassium hydride, sodium hydroxide or potassium hydroxide, sodium t-butoxide or potassium t-butoxide, and if appropriate in the presence of a diluent, such as, for example, tetrahydrofuran or dimethoxyethane, or in a two-phase system of water and an organic solvent, such as, for example, methylene chloride or chloroform at temperatures between 0° C. and 100° C.

A general definition of the sulphonamides also to be used as starting materials in the process (b) according to the invention for preparing compounds of the general formula (I) is given by the formula (V). In the formula (V), R³ preferably or in particular has that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I), as being preferable or particularly preferable for R³.

The starting materials of the formula (V) are known and/or can be prepared by methods known per se (cf. U.S. Pat. No. 4,127,405, U.S. Pat. No. 4,169,719, U.S. Pat. No. 4,371,391, EP-A 7687, EP-A 13480, EP-A 21641, EP-A 23141, EP-A 23422, EP-A 30139, EP-A 35893, EP-A 44808, EP-A 44809, EP-A 48143, EP-A 51466, EP-A 64322, EP-A 70041, EP-A 173312).

A general definition of the sulphonamide derivatives to be used as starting materials in the process (c) according to the invention for preparing compounds of the formula (I) is given by the formula (VI). In the formula (VI), R³ preferably or in particular has that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I), as being preferable or particularly preferable for R³ ; Z preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy or phenoxy, and in particular represents methoxy or phenoxy.

The starting materials of the formula (VI) are known and/or can be prepared by methods known per se.

A general definition of the sulphonyl halides to be used as starting materials in the process (d) according to the invention for preparing compounds of the formula (I) is given by the formula (VII). In the formula (VII), R³ preferably or in particular has that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I), as being preferable or particularly preferable for R³ ; X preferably represents fluorine, chlorine or bromine, and in particular represents chlorine.

The starting materials of the formula (VII) are known and/or can be prepared by methods known per se.

The processes (a), (b), (c) and (d) according to the invention for the preparation of the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate; nitriles, for example acetonitrile and propionitrile; amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.

As reaction auxiliaries and/or as acid acceptors in the processes (a), (b), (c) and (d) according to the invention it is possible to employ all acid-binding agents which can customarily be used for such reactions. Preference is given to alkali metal hydroxides, for example sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, for example calcium hydroxide, alkali metal carbonates and alkoxides, such as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2,2,2]-octane (DABCO).

The reaction temperatures in the processes (a), (b), (c) and (d) according to the invention can be varied within a relatively wide range. The reactions are in general carried out at temperatures of between -20° C. and +100° C., preferably at temperatures between 0° C. and +80° C.

The processes (a), (b), (c) and (d) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

For carrying out processes (a), (b), (c) and (d) according to the invention, the starting materials required in each case are in general employed in approximately equimolar quantities. However, it is also possible to use one of the components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a number of hours at the particular temperature required. Work-up in the case of the processes (a), (b), (c) and (d) according to the invention is in each case carried out by customary methods (cf. the Preparation Examples).

Salts of the compounds of the general formula (I) according to the invention can be prepared if desired. Such salts are obtained in a simple manner by customary methods of forming salts, for example by dissolving or dispersing a compound of the formula (I) in an appropriate solvent, for example methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding an appropriate base. The salts can then--if desired after prolonged stirring--be isolated by concentration or filtration with suction.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial crops, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land. Furthermore, the compounds can be employed for the total control of weeds and for the selective control of weeds in annual crops.

The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.

Additionally, the active compounds according to the invention have a potent microbicidal action and can be practically employed for controlling undesirable microorganisms. The active compounds are suitable for use as crop protection agents, in particular as fungicides.

Fungicides in plant protection are employed for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides in plant protection are employed for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some causative organisms of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:

Xanthomonas species, such as Xanthomonas campestris pv. oryzae;

Pseudomonas species, such as Pseudomonas syringae pv. lachrymans;

Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;

Plasmopara species, such as Plasmopara viticola;

Bremia species, such as Bremia lactucae;

Peronospora species, such as Peronospora pisi or P. brassicae;

Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea

(conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus

(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Sclerotinia species, such as Sclerotinia sclerotiorum;

Tilletia species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

Fusarium species, such as Fusarium culmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum;

Cercospora species, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae;

Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at the concentrations required for controlling plant diseases, permits treatment of aerial parts of plants, of vegetative propagation stock and seeds, and of the soil.

The compounds of the formula (I) are particularly suitable for the protective treatment of pomaceous fruit, such as apples, against the causative organism of powdery mildew in apple (Podosphaera leucotricha) and to a certain extent also for use in rice against Pyricularia oryzae.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. Suitable liquid solvents are in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents are: for example lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, ready-to-use formulations or tank mixes being possible.

Possible components for the mixtures are known herbicides, for example anilides, such as diflufenican and propanil; arylcarboxylic acids, such as dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, such as chloridazon and norflurazon; carbamates, such as chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as mefenacet; sulphonyl-ureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates, such as butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones, such as hexazinone, metamitron and metribuzin; others, such as aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, defenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 2 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

PREPARATION EXAMPLES Example 1 ##STR25## (Process (a))

1.8 g (10 mmol) of 5-(2-fluoro-ethylthio)-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 50 ml of acetonitrile and treated with 2.65 g (11 mmol) of 2-methoxycarbonylphenylsulphonyl isocyanate. The mixture is stirred for 12 hours at 20° C. and then concentrated under reduced pressure. The residue is stirred with isopropanol/petroleum ether (1:1) and crystallized.

3.8 g (91% of theory) of 5-(2-fluoro-ethylthio)-4-methyl-2-(2-methoxy-carbonyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 132° C. are obtained.

By the method of Example 1 and in accordance with the general description of the preparation processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (1) listed in Table 1 below. ##STR26##

                                      TABLE 1                                      __________________________________________________________________________     Examples of compounds of the formula (I)                                       Ex.                                  Melting                                   No.                                                                               R.sup.1 R.sup.2    R.sup.3        point (° C.)                       __________________________________________________________________________      2 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                                  170                                        3 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR27##     144                                        4 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR28##     130                                        5 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR29##     133                                        6 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR30##     151                                        7 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR31##     171                                        8 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR32##     159                                        9 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR33##     137                                       10 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR34##     158                                       11 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR35##     149                                       12 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR36##     153                                       13 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR37##     134                                       14 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR38##     181                                       15 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR39##     121                                       16 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR40##     143                                       17 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR41##     133                                       18 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR42##     147                                       19 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR43##     156                                       20 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR44##     153                                       21 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR45##     157                                       22 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR46##     141                                       23 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR47##      99                                       24 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR48##     116                                       25 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR49##     112                                       26 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR50##     111                                       27 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR51##      89                                       28 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR52##     147                                       29 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR53##     149                                       30 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR54##     130                                       31 CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR55##     169                                       32 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --CCl.sub.2 --CF.sub.3                                                 ##STR56##     151                                       33                                                                                 ##STR57##                                                                             CH.sub.2 --F                                                                               ##STR58##     140                                       34                                                                                 ##STR59##                                                                             CH.sub.2 --Cl                                                                              ##STR60##     152                                       35                                                                                 ##STR61##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR62##     164                                       36                                                                                 ##STR63##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR64##     126                                       37                                                                                 ##STR65##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR66##     143                                       38                                                                                 ##STR67##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR68##     130                                       39                                                                                 ##STR69##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR70##     141                                       40                                                                                 ##STR71##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR72##     134                                       41                                                                                 ##STR73##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR74##     154                                       42                                                                                 ##STR75##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR76##     177                                       43                                                                                 ##STR77##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR78##     138                                       44                                                                                 ##STR79##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR80##     161                                       45                                                                                 ##STR81##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR82##     125                                       46                                                                                 ##STR83##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR84##     106                                       47                                                                                 ##STR85##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR86##     121                                       48                                                                                 ##STR87##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR88##     133                                       49                                                                                 ##STR89##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR90##     155                                       50                                                                                 ##STR91##                                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR92##     147                                       51                                                                                 ##STR93##                                                                             CH.sub.2 --CF.sub.3                                                                        ##STR94##     144                                       52                                                                                 ##STR95##                                                                             CH.sub.2 --CF.sub.3                                                                        ##STR96##      95                                       53                                                                                 ##STR97##                                                                             CH.sub.2 --CF.sub.3                                                                        ##STR98##     182                                       54                                                                                 ##STR99##                                                                             CH.sub.2 --CF.sub.3                                                                        ##STR100##    152                                       55                                                                                 ##STR101##                                                                            CH.sub.2 --CF.sub.3                                                                        ##STR102##    115                                       56                                                                                 ##STR103##                                                                            CH.sub.2 --CF.sub.3                                                                        ##STR104##    117                                       57                                                                                 ##STR105##                                                                            CH.sub.2 --CF.sub.3                                                                        ##STR106##    146                                       58                                                                                 ##STR107##                                                                            CH.sub.2 --CH.sub.2 --F                                                                    ##STR108##    151                                       59                                                                                 ##STR109##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR110##    158                                       60 CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR111##    116                                       61 CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR112##    104                                       62 CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR113##    101                                       63 CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR114##    108                                       64 CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --F                                                                    ##STR115##    118                                       65 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --CF.sub.3                                                             ##STR116##    150                                       66 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --CF.sub.3                                                             ##STR117##    111                                       67 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --CF.sub.3                                                             ##STR118##    148                                       68 CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                                                       ##STR119##    143                                       69 CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                                                       ##STR120##    128                                       70 CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                                                       ##STR121##    136                                       71                                                                                 ##STR122##                                                                            CH.sub.2 --CH.sub.2 --CF.sub.3                                                             ##STR123##    185                                       72                                                                                 ##STR124##                                                                            CH.sub.2 --CH.sub.2 --CF.sub.3                                                             ##STR125##    166                                       73                                                                                 ##STR126##                                                                            CH.sub.2 --CH.sub.2 --CF.sub.3                                                             ##STR127##    165                                       74                                                                                 ##STR128##                                                                            CH.sub.2 --CHF.sub.2                                                                       ##STR129##    169                                       75                                                                                 ##STR130##                                                                            CH.sub.2 --CHF.sub.2                                                                       ##STR131##    154                                       76                                                                                 ##STR132##                                                                            CH.sub.2 --CHF.sub.2                                                                       ##STR133##    138                                       77 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR134##    165                                       78 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR135##    146                                       79 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR136##    145                                       80 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR137##    139                                       81 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR138##    135                                       82 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR139##    121                                       83 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR140##    179                                       84 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR141##    178                                       85 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR142##    171                                       86 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR143##    132                                       87 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR144##    130                                       88 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR145##    140                                       89 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR146##    139                                       90 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR147##    127                                       91 CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR148##    123                                       92                                                                                 ##STR149##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR150##    174                                       93                                                                                 ##STR151##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR152##    132                                       94                                                                                 ##STR153##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR154##    135                                       95                                                                                 ##STR155##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR156##    161                                       96                                                                                 ##STR157##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR158##    144                                       97                                                                                 ##STR159##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR160##    153                                       98                                                                                 ##STR161##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR162##    140                                       99                                                                                 ##STR163##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR164##    167                                       100                                                                                ##STR165##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR166##    171                                       101                                                                                ##STR167##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR168##    180                                       102                                                                                ##STR169##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR170##    152                                       103                                                                                ##STR171##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR172##    123                                       104                                                                                ##STR173##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR174##    124                                       105                                                                                ##STR175##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR176##    172                                       106                                                                                ##STR177##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR178##    132                                       107                                                                               CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR179##    147                                       108                                                                               CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR180##    153                                       109                                                                               CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                        ##STR181##    147                                       110                                                                                ##STR182##                                                                            CH.sub.2 --CF.sub.3                                                                        ##STR183##    128                                       111                                                                                ##STR184##                                                                            CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR185##    129                                       112                                                                                ##STR186##                                                                            CH.sub.2 --CH.sub.2 --F                                                                    ##STR187##    146                                       113                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR188##    164                                       114                                                                               CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                                                    ##STR189##    138                                       115                                                                               CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                                                   ##STR190##    138                                       116                                                                               CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                                                       ##STR191##    144                                       117                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR192##    149                                       118                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR193##    181                                       119                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR194##    180                                       120                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR195##    190                                       121                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR196##    181                                       122                                                                                ##STR197##                                                                            CH.sub.2 --Cl                                                                              ##STR198##    129                                       123                                                                                ##STR199##                                                                            CH.sub.2 --Cl                                                                              ##STR200##    157                                       124                                                                                ##STR201##                                                                            CH.sub.2 --Cl                                                                              ##STR202##    130                                       125                                                                                ##STR203##                                                                            CH.sub.2 --Cl                                                                              ##STR204##    169                                       126                                                                                ##STR205##                                                                            CH.sub.2 --CHF.sub.2                                                                       ##STR206##    158                                       127                                                                               CH.sub.3                                                                               CH.sub.2 --Cl                                                                              ##STR207##    171                                       128                                                                               CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                                                       ##STR208##    166                                       __________________________________________________________________________

The compound listed in Table 1 as Example 58 can, for example, be prepared as follows: ##STR209## (Process (b))

1.07 g (5 mmol) of 2-allyloxy-benzenesulphonamide are dissolved in 25 ml of acetonitrile and admixed with 0.8 g (5.3 mmol) of diazabicycloundecene (DBU) with stirring. After 30 minutes at 20° C., 1.62 g (5 mmol) of 4-cyclopropyl-5-(2-fluoro-ethylthio)-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one are added and the mixture is stirred for a further 12 hours. The reaction mixture is then poured into ice water, acidified with 10% strength hydrochloric acid and extracted twice with methylene chloride. The residue obtained after drying with magnesium sulphate and concentrating under reduced pressure is crystallized from ether.

1.4 g (63% of theory) of 2-(2-allyloxy-phenylsulphonyl-aminocarbonyl)-4-cyclopropyl-5-(2-fluoro-ethylthio)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 151° C. are obtained.

The compound listed in Table 1 as Example 59 can, for example, be prepared as follows ##STR210## (Process (d))

A mixture of 4.4 g (20 mmol) of 5-(2-chloro-ethylthio)-4-cyclopropyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 7.6 g (24 mmol) of 2-(N-methoxy-N-methyl-aminosulphonyl)-benzene-sulphonyl chloride, 2.6 g (40 mmol) of sodium cyanate and 1.2 g (15 mmol) of pyridine in 50 ml of acetonitrile is stirred at 20° C. for 48 hours. The mixture is then concentrated under reduced pressure and the oily residue is taken up in methylene chloride and washed with 10% strength hydrochloric acid. The organic phase is dried with magnesium sulphate and concentrated under reduced pressure, and the residue obtained is crystallized from methanol/isopropanol.

4.7 g(45% of theory) of 5-(2-chloroethylthio)-4-cyclopropyl-2-[2-N-methoxy-N-methyl-aminosulphonyl)-phenylsulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 158° C. are obtained.

Starting materials of the formula (II)

Example (II-1) ##STR211##

6.6 g (0.05 mol) of 5-mercapto-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 40 ml of water and 40 ml of dioxane and admixed with 10 g (0.25 mol) of sodium hydroxide. With vigorous stirring, a gentle stream of frigen 22 (difluorochloromethane) is passed through the mixture at 80° C. for 16 hours. The solution is allowed to cool, adjusted to a weakly acidic pH using 10% strength hydrochloric acid and then extracted repeatedly with ethyl acetate. The combined organic phases are dried with magnesium sulphate, filtered and concentrated under reduced pressure. The residue is crystallized from diethyl ether.

0.7 g (7.7% of theory) of 5-difluoromethylthio-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 87° C. is obtained.

Example (II-2) ##STR212##

35.1 g (0.18 mol) of the potassium salt of 5-mercapto-4-allyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 200 ml of methanol, admixed with 22.9 g (0.18 mol) of 1-bromo-2-fluoro-ethane and stirred at 20° C. for 12 hours. The mixture is then stirred for another 4 hours at 60° C., cooled and concentrated under reduced pressure. The residue is taken up in methylene chloride and washed with 10% strength hydrochloric acid and water. The residue is concentrated under reduced pressure, stirred with petroleum ether and crystallized.

After filtration under suction and drying, 24.8 g (67.9% of theory) of 4-allyl-5-(2-fluoroethylthio)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 65° C. are obtained.

By the methods of Examples (II-1) and (II-2), it is also possible to prepare, for example, the compounds of the formula (II) listed in Table 2 below. ##STR213##

                  TABLE 2                                                          ______________________________________                                         Examples of compounds of the formula (II)                                      Ex.                             Melting                                        No.  R.sup.1     R.sup.2        point (° C.)                            ______________________________________                                         II-3 CH.sub.3    CH.sub.2 --CF.sub.3                                                                           132                                            II-4 CH.sub.3    CH.sub.2 --CH.sub.2 --CCl.sub.2 --CF.sub.3                                                    121                                            II-5 CH.sub.3    CH.sub.2 --CH.sub.2 --F                                                                        88                                            II-6                                                                                            CH.sub.2 --F   116                                            II-7                                                                                 ##STR214## CH.sub.2 --Cl  130                                            II-8                                                                                 ##STR215## CH.sub.2 --CH.sub.2 --F                                                                       120                                            II-9                                                                                 ##STR216## CH.sub.2 --CF.sub.3                                                                           126                                            II-10                                                                               CH.sub.3    CH.sub.2 --CHF.sub.2                                                                           95                                            II-11                                                                               CH.sub.3    CH.sub.2 --CH.sub.2 --CF.sub.3                                                                144                                            II-12                                                                                ##STR217## CHF.sub.2                                                     II-13                                                                                ##STR218## CH.sub.2 --CHF.sub.2                                                                          111                                            II-14                                                                                ##STR219## CH.sub.2 --CH.sub.2 --CF.sub.3                                                                127                                            II-15                                                                               CH.sub.3    CH.sub.2 --F                                                  II-16                                                                               CH.sub.3    CH.sub.2 --Cl  113                                            II-17                                                                                ##STR220## CF.sub.3                                                      II-18                                                                               CH.sub.3    CF.sub.3                                                      II-19                                                                               C.sub.2 H.sub.5                                                                            CF.sub.3                                                      II-20                                                                               CH.sub.2 --CH═CH.sub.2                                                                 CF.sub.3                                                      II-21                                                                               CH.sub.2 --CH═CH.sub.2                                                                 CH.sub.2 --CHF.sub.2                                          II-22                                                                               CH.sub.2 --CH═CH.sub.2                                                                 CH.sub.2 --CF.sub.3                                           II-23                                                                                ##STR221## CF.sub.3                                                      II-24                                                                                ##STR222## CHF.sub.2                                                     II-25                                                                                ##STR223## CH.sub.2 --F                                                  II-26                                                                                ##STR224## CH.sub.2 --CH.sub.2 --F                                       II-27                                                                                ##STR225## CH.sub.2 --CHF.sub.2                                          II-28                                                                                ##STR226## CH.sub.2 --CF.sub.3                                           II-29                                                                               CH.sub.3    CH.sub.2 --CH.sub.2 --Cl                                                                      124                                            II-30                                                                               CH.sub.2 --CH═CH.sub.2                                                                 CH.sub.2 --CH.sub.2 --Cl                                      II-31                                                                                ##STR227## CH.sub.2 --CH.sub.2 --Cl                                                                      121                                            II-32                                                                                ##STR228## CH.sub.2 --CH.sub.2 --Cl                                      II-33                                                                               NH.sub.2    CH.sub.2 --F                                                  II-34                                                                               NH.sub.2    CH.sub.2 --Cl                                                 II-35                                                                               NH.sub.2    CH--F.sub.2                                                   II-36                                                                               NH.sub.2    CF.sub.3                                                      II-37                                                                               NH.sub.2    CH.sub.2 --CH.sub.2 --F                                       II-38                                                                               NH.sub.2    CH.sub.2 --CH.sub.2 --Cl                                      II-39                                                                               NH.sub.2    CH.sub.2 --CHF.sub.2                                          II-40                                                                               NH.sub.2    CH.sub.2 --CF.sub.3                                           II-41                                                                               NH--CH.sub.3                                                                               CH.sub.2 --F                                                  II-42                                                                               NH--CH.sub.3                                                                               CH.sub.2 --Cl                                                 II-43                                                                               NH--CH.sub.3                                                                               CF.sub.3                                                      II-44                                                                               NH--CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --F                                       II-45                                                                               NH--CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                                      II-46                                                                               NH--CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                          II-47                                                                               NH--CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                           II-48                                                                               N(CH.sub.3).sub.2                                                                          CH.sub.2 --F                                                  II-49                                                                               N(CH.sub.3).sub.2                                                                          CH.sub.2 --Cl                                                 II-50                                                                               N(CH.sub.3).sub.2                                                                          CHF.sub.2                                                     II-51                                                                               N(CH.sub.3).sub.2                                                                          CF.sub.3                                                      II-52                                                                               N(CH.sub.3).sub.2                                                                          CH.sub.2 --CH.sub.2 --F                                       II-53                                                                               N(CH.sub.3).sub.2                                                                          CH.sub.2 --CH.sub.2 --Cl                                      II-54                                                                               N(CH.sub.3).sub.2                                                                          CH.sub.2 --CHF.sub.2                                          II-55                                                                               N(CH.sub.3).sub.2                                                                          CH.sub.2 --CF.sub.3                                           II-56                                                                               CH.sub.3    CH.sub.2 --CHBr--CF.sub.3                                     II-57                                                                               CH.sub.3    CH.sub.2 --CF.sub.2 --CHF--CF.sub.3                                                           .sup.1 H NMR (CDCl.sub.3.                                                      δ): 3.28(s,                                                              N--CH.sub.3). 3.70                                                             (br, t, S--CH. 4.9-                                                            5.2(m, CHF) ppm                                II-58                                                                               CH.sub.3    CH.sub.2 --CF.sub.2 --CHF.sub.2                                                               .sup.1 H NMR (CDCl.sub.3,                                                      δ): 3.28(s,                                                              N--CH.sub.3),                                                                  3.66(t, S--CH.sub.2,                                                           5.90(tt, CHF.sub.2) ppm                        ______________________________________                                    

Starting materials of the formula (IV):

Example(IV-1) ##STR229##

3.44 g (22 mmol) of phenyl chloroformate are added dropwise with efficient stirring to a mixture of 3.54 g (20 mmol) of 5-(2-fluoro-ethylthio)-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 0.9 g (22 mmol) of sodium-hydroxide, 0.1 g (0.3 mmol) of tetrabutylammonium bromide, 30 ml of water and 40 ml of methylene chloride, and the mixture is stirred for a further 12 hours. The organic phase is separated off, washed with water, dried with magnesium sulphate and concentrated under reduced pressure, and the residue obtained is crystallized from ether.

5.1 g (86% of theory) of 5-(2-fluoro-ethylthio)-4-methyl-2-phenoxy-carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 106° C. are obtained.

By the method of Example (IV-1), it is also possible to prepare, for example, the compounds of the formula (IV) listed in Table 3 below: ##STR230##

                                      TABLE 3                                      __________________________________________________________________________     Examples of compounds of the formula (IV)                                      Ex. No.                                                                            Z              R.sup.1 R.sup.2    Mp. (° C.)                        __________________________________________________________________________     IV-2                                                                                               ##STR231##                                                                            CH.sub.2 --CF.sub.3                                                                       121                                      IV-3                                                                                ##STR232##                                                                                    ##STR233##                                                                            CH.sub.2 --CH.sub.2 --F                                                                   129                                      IV-4                                                                                ##STR234##    CH.sub.3                                                                               CH.sub.2 --CF.sub.3                                                                       114                                      IV-5                                                                                ##STR235##    CH.sub.3                                                                               CH.sub.2 --CHF.sub.2                                IV-6                                                                                ##STR236##    CH.sub.3                                                                               CH.sub.2 --F                                        IV-7                                                                                ##STR237##    CH.sub.3                                                                               CHF.sub.2                                           IV-8                                                                                ##STR238##                                                                                    ##STR239##                                                                            CHF.sub.2                                           IV-9                                                                                ##STR240##                                                                                    ##STR241##                                                                            CF.sub.3                                            IV-10                                                                               ##STR242##                                                                                    ##STR243##                                                                            CH.sub.2 --CHF.sub.2                                IV-11                                                                               ##STR244##                                                                                    ##STR245##                                                                            CH.sub.2 --CH.sub.2 --CF.sub.3                      IV-12                                                                               ##STR246##                                                                                    ##STR247##                                                                            CH.sub.2 --CF.sub.2 --CHF.sub.2                     IV-13                                                                               ##STR248##    CH.sub.3                                                                               CF.sub.3                                            IV-14                                                                               ##STR249##    CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --F                             IV-15                                                                               ##STR250##    CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --CCl.sub.2 --CF.sub.3          IV-16                                                                               ##STR251##                                                                                    ##STR252##                                                                            CH.sub.2 --F                                        IV-17                                                                               ##STR253##                                                                                    ##STR254##                                                                            CH.sub.2 --Cl                                       IV-18                                                                               ##STR255##    CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --CF.sub.3                      IV-19                                                                               ##STR256##    CH.sub.3                                                                               CH.sub.2 --Cl                                       IV-20                                                                               ##STR257##    C.sub.2 H.sub.5                                                                        CF.sub.3                                            IV-21                                                                               ##STR258##    CH.sub.2 --CH═CH.sub.2                                                             CF.sub.3                                            IV-22                                                                               ##STR259##    CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CHF.sub.2                                IV-23                                                                               ##STR260##    CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CF.sub.3                                 IV-24                                                                               ##STR261##                                                                                    ##STR262##                                                                            CF.sub.3                                            IV-25                                                                               ##STR263##                                                                                    ##STR264##                                                                            CHF.sub.2                                           IV-26                                                                               ##STR265##                                                                                    ##STR266##                                                                            CH.sub.2 F                                          IV-27                                                                               ##STR267##                                                                                    ##STR268##                                                                            CH.sub.2 --Cl                                       IV-28                                                                               ##STR269##                                                                                    ##STR270##                                                                            CH.sub.2 --CH.sub.2 --F                             IV-29                                                                               ##STR271##                                                                                    ##STR272##                                                                            CH.sub.2 --CHF.sub.2                                IV-30                                                                               ##STR273##                                                                                    ##STR274##                                                                            CH.sub.2 --CF.sub.3                                 IV-31                                                                               ##STR275##                                                                                    ##STR276##                                                                            CH.sub.2 --CH.sub.2 --Cl                            IV-32                                                                               ##STR277##    CH.sub.3                                                                               CH.sub.2 --CH.sub.2 --Cl                            IV-33                                                                               ##STR278##    C.sub.2 H.sub.5                                                                        CH.sub.2 --CH.sub.2 --Cl                            IV-34                                                                               ##STR279##                                                                                    ##STR280##                                                                            CH.sub.2 --CH.sub.2 --Cl                            IV-35                                                                               ##STR281##    CH.sub.2 --CH═CH.sub.2                                                             CH.sub.2 --CH.sub.2 --Cl                            IV-36                                                                               ##STR282##    NH.sub.2                                                                               CH.sub.2 --F                                        IV-37                                                                               ##STR283##    NH.sub.2                                                                               CH.sub.2 --Cl                                       IV-38                                                                               ##STR284##    NH.sub.2                                                                               CHF.sub.2                                           IV-39                                                                               ##STR285##    NH.sub.2                                                                               CF.sub.3                                            IV-40                                                                               ##STR286##    NH.sub.2                                                                               CH.sub.2 --CH.sub.2 --F                             IV-41                                                                               ##STR287##    NH.sub.2                                                                               CH.sub.2 --CH.sub.2 --Cl                            IV-42                                                                               ##STR288##    NH.sub.2                                                                               CH.sub.2 --CHF.sub.2                                IV-43                                                                               ##STR289##    NH.sub.2                                                                               CH.sub.2 --CF.sub.3                                 IV-44                                                                               ##STR290##    NH--CH.sub.3                                                                           CH.sub.2 --F                                        IV-45                                                                               ##STR291##    NH--CH.sub.3                                                                           CH.sub.2 --Cl                                       IV-46                                                                               ##STR292##    NH--CH.sub.3                                                                           CHF.sub.2                                           IV-47                                                                               ##STR293##    NH--CH.sub.3                                                                           CF.sub.3                                            IV-48                                                                               ##STR294##    NH--CH.sub.3                                                                           CH.sub.2 --CH.sub.2 --F                             IV-49                                                                               ##STR295##    NH--CH.sub.3                                                                           CH.sub.2 --CH.sub.2 --Cl                            IV-50                                                                               ##STR296##    NH--CH.sub.3                                                                           CH.sub.2 --CHF.sub.2                                IV-51                                                                               ##STR297##    NH--CH.sub.3                                                                           CH.sub.2 --CF.sub.3                                 IV-52                                                                               ##STR298##    N--(CH.sub.3).sub.2                                                                    CH.sub.2 --F                                        IV-53                                                                               ##STR299##    N--(CH.sub.3).sub.2                                                                    CH.sub.2 --Cl                                       IV-54                                                                               ##STR300##    N--(CH.sub.3).sub.2                                                                    CHF.sub.2                                           IV-55                                                                               ##STR301##    N--(CH.sub.3).sub.2                                                                    CF.sub.3                                            IV-56                                                                               ##STR302##    N--(CH.sub.3).sub.2                                                                    CH.sub.2 --CH.sub.2 --F                             IV-57                                                                               ##STR303##    N--(CH.sub.3).sub.2                                                                    CH.sub.2 --CH.sub.2 --Cl                            IV-58                                                                               ##STR304##    N--(CH.sub.3).sub.2                                                                    CH.sub.2 --CHF.sub.2                                IV-59                                                                               ##STR305##    N--(CH.sub.3).sub.2                                                                    CH.sub.2 --CF.sub.3                                 IV-60                                                                               ##STR306##    CH.sub.3                                                                               CH.sub.2 --CHBr--CF.sub.3                           IV-61                                                                               ##STR307##    CH.sub.3                                                                               CH.sub.2 --CF.sub.2 --CHF--CF.sub.3                 IV-62                                                                               ##STR308##    CH.sub.3                                                                               CH.sub.2 --CF.sub.2 --CHF.sub.2                     __________________________________________________________________________

Use examples:

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil. After 24 hours, the soil is watered with the preparation of the active compound. It is advantageous to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is not critical, only the amount of active compound applied per unit area being decisive. After 3 weeks, the degree of damage to the plants is rated in per cent damage in comparison to the development of the untreated control. The figures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, the compounds according to Preparation Examples 5, 11, 17, 18, 21, 25, 33, 34, 35, 36, 37, 38, 39, 40, 43, 48, 49, 51, 52, 53, and 54, for example, exhibit a strong action against weeds.

                                      TABLE A                                      __________________________________________________________________________     Pre-emergence test/greenhouse                                                  Compound                                                                       of                                                                             Preparation                                                                          Applica-                                                                 Example                                                                              tion rate   Ama- Galin-                                                                             Matri-                                              No.   g/ha Bromus                                                                             Poa                                                                               ranthus                                                                             soga                                                                               caria                                                                              Portulaca                                                                           Viola                                      __________________________________________________________________________     51    250  95  95 95   95  100 95   95                                         34    125  80  95 95   95  100 100  90                                         52    125  80  -- 90   95  90  60   --                                         53    125  90  -- 90   95  90  80   80                                         54    125  90  -- 90   95  80  --   60                                         33    125  95  95 95   95  95  95   90                                         17    125  95  95 95   95  95  100  95                                         18    125  95  90 80   90  60  --   95                                         21    125  80  80 90   95  95  90   95                                         25    125  95  90 95   95  95  100  90                                         5     125  95  95 95   90  80  95   90                                         11    125  80  70 95   95  95  95   95                                         35    125  95  95 95   95  95  95   95                                         36    125  50  80 95   100 --  95   90                                         37    125  95  60 95   100 95  100  95                                         38    125  80  60 95   100 100 90   95                                         39    125  95  95 95   95  95  100  95                                         40    125  60  -- 95   95  80  80   --                                         43    125  80  70 95   100 95  95   95                                         48    125  95  95 95   95  95  95   70                                         49    125  90  95 95   95  95  80   90                                         __________________________________________________________________________

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are employed in 2000 1 of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.

The figures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, the compounds of Preparation Examples 5, 8, 10, 11, 17, 33, 34, 38, 39, 48, 49, 51, 52, 53 and 54, for example, show a strong action against weeds.

                                      TABLE B                                      __________________________________________________________________________     Post-emergence test/greenhouse                                                 Compound of Preparation                                                                    Application                                                                          Amaran-                                                                             Am- Helian-                                                                            Matri-                                                                             Sola-                                                                             Stella-                                                                               Xan-                              Example No. rate g/ha                                                                            thus brosia                                                                             thus                                                                               caria                                                                              num                                                                               ria Viola                                                                             thium                             __________________________________________________________________________     51          125    95  90  100 95  95 70  80 95                                34           60   100  95  100 95  100                                                                               90  100                                                                               100                               52          250   --   80  100 90  70 95  60  80                               53          250   --   95  100 95  95 95  95  90                               54          125    95  90  100 80  95 70  90  90                               33           60   100  90  100 95  100                                                                               95  90 --                                17           60    90  90   80 50  80 70  50  90                                5          125    95  90   80 95  95 90  --  95                                8          125   100  70  100 95  95 100 100                                                                               100                               10          125   100  --  --  --  95 90  --  90                               11          125   100  60  --  --  100                                                                               95  60  90                               38          125    95  95   95 70  90 95  95  80                               39          125   100  90  100 95  95 95  95 100                               48          125    95  80   80 80  90 --  90  70                               49          125   100  90  100 90  80 --  95  70                               __________________________________________________________________________

Example C

Podosphaera test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of allylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound. After the spray coating has dried on, the plants are inoculated by dusting with conidiae of the causative organism of apple mildew (Podosphaera leucotricha).

The plants are then placed in a greenhouse at 23° C. and a relative atmospheric humidity of about 70%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compounds of Preparation Examples 34 and 51, for example, have an efficacy of 98 to 100% at an active compound concentration of 100 ppm.

                                      TABLE C                                      __________________________________________________________________________     Podosphaera test (apple)/protective                                                                        Efficacy in % of the                                                           untreated control at an                                                        active compound                                    Active compound             concentration of 100 ppm                           __________________________________________________________________________      ##STR309##                  98                                                 ##STR310##                 100                                                __________________________________________________________________________ 

What is claimed is:
 1. A compound of the formula (II) ##STR311## in which R¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or propenyl, butenyl, or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,R² represents fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl. 